CN101679601A - Novel phosphorus-containing Resins, epoxy, with this Resins, epoxy as composition epoxy resin and cured article thereof that must composition - Google Patents
Novel phosphorus-containing Resins, epoxy, with this Resins, epoxy as composition epoxy resin and cured article thereof that must composition Download PDFInfo
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- CN101679601A CN101679601A CN200880007011A CN200880007011A CN101679601A CN 101679601 A CN101679601 A CN 101679601A CN 200880007011 A CN200880007011 A CN 200880007011A CN 200880007011 A CN200880007011 A CN 200880007011A CN 101679601 A CN101679601 A CN 101679601A
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 71
- 229920005989 resin Polymers 0.000 title claims abstract description 59
- 239000011347 resin Substances 0.000 title claims abstract description 59
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 42
- 239000011574 phosphorus Substances 0.000 title claims abstract description 39
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000003822 epoxy resin Substances 0.000 title claims description 40
- 229920000647 polyepoxide Polymers 0.000 title claims description 40
- 239000000203 mixture Substances 0.000 title claims description 25
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 30
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 20
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims abstract description 20
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 20
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 15
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 10
- 239000004305 biphenyl Substances 0.000 claims abstract description 10
- 239000012778 molding material Substances 0.000 claims abstract description 9
- 239000003566 sealing material Substances 0.000 claims abstract description 9
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 21
- 235000019587 texture Nutrition 0.000 claims description 12
- -1 phosphorus compound Chemical class 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052802 copper Inorganic materials 0.000 abstract description 7
- 239000010949 copper Substances 0.000 abstract description 7
- 238000003825 pressing Methods 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- 239000012777 electrically insulating material Substances 0.000 abstract description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 12
- 239000003063 flame retardant Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 150000000191 1,4-naphthoquinones Chemical class 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 9
- 239000004843 novolac epoxy resin Substances 0.000 description 7
- 229940058344 antitrematodals organophosphorous compound Drugs 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 150000002903 organophosphorus compounds Chemical class 0.000 description 5
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical class C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 150000004780 naphthols Chemical class 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000004437 phosphorous atom Chemical group 0.000 description 3
- 150000004053 quinones Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 150000004782 1-naphthols Chemical class 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- JHYNXXDQQHTCHJ-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 JHYNXXDQQHTCHJ-UHFFFAOYSA-M 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000005328 phosphinyl group Chemical group [PH2](=O)* 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/304—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Laminated Bodies (AREA)
Abstract
Novel phosphorus-containing Resins, epoxy shown in the general formula (1) with naphthalene skeleton, a:1,2,3,4,5,6, b:1,2,3,4,5,6,7, c:0,1,2,3 ..., (X) expression benzene, naphthalene, anthracene, phenanthrene, biphenyl, (Y) for example represent general formula (3), d:0 or 1, R1, R2 represent alkyl, can be straight chain shape, a chain, ring-type, in addition, R1 can be in conjunction with forming ring texture with R2.This Resins, epoxy is suitable as with the copper plate pressing plate that uses in the electronic circuit board electrically insulating material as representative, and the sealing material that uses in the electronic component, formed material, cast-molding material, caking agent, film also are suitable as the electrical insulating coating material.
Description
Technical field
The present invention relates to can be used as the resin combination that is used for making the copper plate pressing plate that electronic circuit board uses, or the sealing material that uses in the electronic component, formed material, cast-molding material (notes section bar), caking agent, electrical insulating coating are with novel phosphorus-containing Resins, epoxy, composition epoxy resin and the cured article thereof of material etc.
Background technology
Resins, epoxy is widely used in electronic component, electronic machine, trolley part, FRP, the sporting goods etc. owing to cementability, thermotolerance, formability excellence.Wherein, because copper plate pressing plate or the sealing material strong request of using in electronic component, the electronic machine prevented, postpones securities such as fire, use up to now has the brominated epoxy resin of these characteristics etc.Though exist than problem such as great, owing to give flame retardant resistance by importing halogen, particularly bromine to Resins, epoxy, and epoxy group(ing) has hyperergy, obtains the cured article of excellence, and the brominated epoxy resin class is positioned as useful electronics, electricity material.But, observe nearest electronic machine, pay attention to so-called compact trend most and strengthen gradually.Under this social requirement, heavy halogenide considers it is preferable material not from nearest lightweight trend aspect, in addition, during life-time service, produces halid dissociating under the high temperature, might produce wiring thus and corroding.Further, produce objectionable impuritiess such as halogenide when the electronic component that uses, electronic machine burning, consider that from the environmental safety aspect utilization of halogen becomes problem, and its equivalent material is studied.The inventor furthers investigate this problem, has invented compactization or the wiring corrosive problem of no electronic machine, does not produce deleterious halid phosphorous epoxy resin.(patent documentation 1～2) still further requires the thermotolerance raising of cured article or the reduction of water-intake rate etc.
Patent documentation 1: Japanese kokai publication hei 11-166035
Patent documentation 2: Japanese kokai publication hei 11-279258
Summary of the invention
The inventor has given the phosphorous epoxy resin of flame retardant resistance in order to realize not using halogen thermotolerance further improves or water-intake rate further reduces and further investigate, discovery is by importing the novel phosphorus-containing Resins, epoxy that specific skeleton is the naphthalene skeleton, do not damage flame retardant resistance and can reduce phosphorous rate.Owing to can reduce phosphorous rate, obtain thermotolerance height, cured article that water-intake rate is low, thereby finish the present invention.In the past as thermotolerance or water-proof modification method, there is the method that imports the naphthalene skeleton, but the naphthols novolac epoxy resin can not reach purpose of the present invention, finds that the specific Resins, epoxy that contains the naphthalene skeleton of general formula (7) can reach purpose of the present invention.In addition, in having the specific Resins, epoxy of naphthalene skeleton, exist solvent solubility poor, separate out the crystalline material, can not prepare varnish during the preparation prepreg.But, neo-epoxy resin of the present invention, Resins, epoxy that can be by having the naphthalene skeleton and the organo phosphorous compounds shown in general formula (8) and/or the general formula (9) react and significantly improve solvent solubility, can separate out with no crystal, stable varnish prepares prepreg.The objective of the invention is to, provide the copper plate that is suitable for using in electronic circuit board pressing plate, novel phosphorus-containing Resins, epoxy, phosphorous epoxy resin composition and cured article thereof in the sealing material that uses in the electronic component, formed material, cast-molding material, caking agent, electrical insulating coating material, the electrical insulating film etc.
That is, main points of the present invention are, the novel phosphorus-containing Resins, epoxy, phosphorous epoxy resin composition and the cured article thereof that contain the naphthalene skeleton shown in the general formula (1).
a：1、2、3、4、5、6，
b：1、2、3、4、5、6、7，
c：0、1、2、3、......，
(X) expression benzene, naphthalene, anthracene, phenanthrene, biphenyl.
(Y) expression general formula (2)～(4), at least 1 (Y) is general formula (3) or general formula (4) in 1 molecule.
D:0 or 1,
R1, R2 represent alkyl, can be straight chain shape, a chain, ring-type.In addition, R1 can be in conjunction with forming ring texture with R2.
e：0、1、2、3、4、5、6，
b：1、2、3、4、5、6、7，
g：1、2、3......，
D:0 or 1,
f：1、2、3、4、5、6，
f+e≤6
R1, R2 represent alkyl, can be straight chain shape, a chain, ring-type.In addition, R1 can be in conjunction with forming ring texture with R2.
(X) expression benzene, naphthalene, anthracene, phenanthrene, biphenyl.
(Y) expression general formula 2～4.
(Z) expression general formula 5, general formula 6.
h：0、1、2、3，
R3: the expression alkyl can be straight chain shape, a chain, ring-type.
i：0、1、2、3、4、5，
R3: the expression alkyl can be straight chain shape, a chain, ring-type.
Further, novel phosphorus-containing Resins, epoxy, phosphorous epoxy resin composition and the cured article thereof of above-mentioned flame retardant resistance is used for the manufacturing resin combination of the copper plate pressing plate that electronic circuit board uses, and the sealing material that uses in the electronic component, formed material, cast-molding material, caking agent, electrical insulating coating are with in material etc.
Description of drawings
Fig. 1 is the GPC figure of the Resins, epoxy that obtains among the embodiment 2.
Fig. 2 is the FTIR figure of the Resins, epoxy that obtains among the embodiment 2.
Embodiment
The present invention is carried out specific description.
The novel phosphorus-containing Resins, epoxy with naphthalene skeleton shown in the general formula of the present invention (1) reacts by the phosphorus compound class shown in the Resins, epoxy shown in the general formula (7) and general formula (8) and/or the general formula (9) and obtains.
a：1、2、3、4、5、6，
b：1、2、3、4、5、6、7，
c：0、1、2、3、......，
(X) expression benzene, naphthalene, anthracene, phenanthrene, biphenyl.
D:0 or 1,
R1, R2 represent alkyl, can be straight chain shape, a chain, ring-type.In addition, R1 can be in conjunction with forming ring texture with R2.
D:0 or 1,
R1, R2 represent alkyl, can be straight chain shape, a chain, ring-type.In addition, R1 can be in conjunction with forming ring texture with R2.
(Z) expression general formula 5, general formula 6.
As the Resins, epoxy shown in the general formula (7), can enumerate Japanese kokai publication hei 03-000717, Japanese kokai publication hei 03-090075, TOHKEMY 2006-160868, the Resins, epoxy of putting down in writing among the TOHKEMY 2004-123859 etc., can enumerate for example ESN-155 of ESN-100 series, ESN-185V, ESN-175 (Toto Kasei KK's system Beta Naphthol 99MIN aralkyl-type epoxy resin), the ESN-355 of ESN-300 series, ESN-375 (Toto Kasei KK's system bisnaphthol aralkyl-type epoxy resin), the ESN-475V of ESN-400 series, ESN-485 (the system α of Toto Kasei KK naphthols aralkyl-type epoxy resin), but be not limited thereto.In addition, also can use two or more.In addition, in the scope that does not influence rerum natura, can also use other epoxy resin.
Organo phosphorous compounds class shown in the general formula that uses among the present invention (8) refer to can with the active hydrogen and the phosphorus atom bonded organo phosphorous compounds class of functional group reactionses such as quinones or glycidyl, vinyl, specifically, can enumerate HCA (three photochemistry Co., Ltd. systems 9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound), oxidation diphenylphosphine, CPHO (Nippon Chemical Ind's system, inferior ring octyl group phosphine oxide) etc.Organo phosphorous compounds class shown in the general formula that uses among the present invention (9) refers to the active hydrogen of the organo phosphorous compounds class shown in the general formula (8) and the phosphorous phenolic compound that the quinones reaction obtains, specifically, can enumerate HCA-HQ (the system 10-(2 of three photochemistry Co., Ltd., the 5-dihydroxy phenyl)-and the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound), 10-(2,7-dihydroxyl naphthyl)-and the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound), PPQ (Hokko Chemical Industry Co., Ltd.'s system two phenenyl phosphinyl quinhydrones), the two phenenyl phosphinyl naphthoquinones, CPHO-HQ (the inferior ring of Nippon Chemical Ind's system octyl group phosphinyl-1, the 4-Benzenediol), inferior ring octyl group phosphinyl-1,4-naphthalene glycol etc.So long as the compound shown in general formula (8) and/or the general formula (9) gets final product, they are not limited especially among the present invention, in addition, can also use two or more.
React the phosphorous phenolic compound shown in the general formula (9) that obtains with phosphorus atom bonded active hydrogen and quinones, for example by Japanese kokai publication hei 5-214068 communique, Muscovite common magazine (Zh.Obshch.Khim.), 42 (11), the method shown in 2415-2418 page or leaf (1972), Japanese kokai publication sho 60-126293 communique, Japanese kokai publication sho 61-236787 communique, the Japanese kokai publication hei 5-331179 communique obtains.At this moment, in order only to take out the polyfunctional phosphorous phenolic compound that generates, be necessary to carry out operations such as purifying or recrystallization.But if the compound of residual general formula (8) suitably, promptly active hydrogen and phosphorus atom bonded organo phosphorous compounds then not only need not this operation, but also can improve the phosphorus content of Resins, epoxy, reduce reacted Resins, epoxy viscosity simultaneously.
The reaction of the phosphorus compound of the Resins, epoxy that contains the naphthalene skeleton of general formula (7) and general formula (8) and/or general formula (9) can be undertaken by known method, can under agitation carry out under 100 ℃～200 ℃, more preferably 120 ℃～180 ℃ temperature of reaction.
The mensuration that reaction times can be carried out epoxy equivalent (weight) decides.Mensuration can be measured by the method for JIS K7236.The reaction of the Resins, epoxy that contains the naphthalene skeleton by general formula (7) and the phosphorus compound of general formula (8) and/or general formula (9), epoxy equivalent (weight) increases, by with theoretical epoxy equivalent (weight) relatively, can determine reaction end.
In addition, when speed of response is slow, can use catalyzer to realize productive improvement as required.Specifically, can use tertiary amines such as benzyl dimethyl amine, quaternary ammonium salts such as tetramethyl ammonium chloride, triphenylphosphine, three (2, the 6-Dimethoxyphenyl) phosphine class such as phosphine, phosphonium salt classes such as ethyl triphenyl phosphonium bromide, various catalyzer such as imidazoles such as glyoxal ethyline, 2-ethyl-4-methylimidazole.
Solidifying agent as the present composition, can use with various polyphenol resenes or the anhydrides of phenol novolac resin as representative, with DICY is the amine of representative, the hydrazides class, normally used hardener for epoxy resin such as acid polyester, these solidifying agent can only use a kind or use two or more.
In the composition of the present invention, can cooperate curing catalysts such as tertiary amine, quaternary ammonium salt, phosphine class, imidazoles as required.In addition, can also cooperate strongtheners such as inorganic filler or woven fiber glass Kevlar as required, packing material, pigment etc.
The characteristic of using the veneer sheet that novel phosphorus-containing Resins, epoxy of the present invention obtains is estimated, and the result is that thermotolerance height and water-intake rate are low, do not conform to the composition epoxy resin or its cured article that have halogenide just can obtain flame retardant resistance.This Resins, epoxy, composition epoxy resin and cured article thereof can be used as the resin combination that is used for making the copper plate pressing plate that electronic circuit board uses, and the sealing material that uses in the electronic component, formed material, cast-molding material, caking agent, mould material, electrical insulating coating are with material etc.
Embodiment
Enumerate embodiment and comparative example the present invention is carried out specific description, but the present invention is not limited by them.Veneer sheet is by following condition manufacturing.The Resins, epoxy that obtains, solidifying agent, the curing catalyst that uses as required are dissolved in the solvent, are infiltrated up in the woven fiber glass.Carry out drying except that desolvating, obtain prepreg.4 prepregs of lamination and Copper Foil obtain the cured article of veneer sheet by hot pressing.Flame retardant resistance is measured according to UL (Underwriter Laboratorics) standard.The Copper Foil stripping strength is measured according to JIS C 64815.7.In addition, the second-order transition temperature of cured article is measured by the system Exster6000DSC of エ ス エ ス ア イ Na ノ テ Network ノ ロ ジ one Co., Ltd..Will by in the initial stage weight under the condition of 85 ℃ * humidity of temperature 85% and the weight after through 500 hours obtain gain in weight to liken to and be water-intake rate.
Embodiment 1
Add the HCA of 56.1 weight parts and the toluene of 131 weight parts in the separable flask of four neck glass with whipping appts, thermometer, cooling tube, nitrogen gatherer, heating makes their dissolvings.Then, 1 of 39.0 weight parts are dropped into, the 4-naphthoquinones in the marginal not meaning intensification limit that reaction heat caused in batches.This moment 1, the mol ratio of 4-naphthoquinones and HCA is 1,4-naphthoquinones/HCA=0.95.After the reaction, add the ESN-485 of 254.5 weight parts, the limit imports the nitrogen limit and stirs, be heated to 130 ℃ with toluene except that going to system.Add the triphenylphosphine of 0.1 weight part, reacted 4 hours down at 160 ℃.The epoxy equivalent (weight) of the Resins, epoxy that obtains is 349.6g/eq, and phosphorus content is 0.80 weight %.In the Resins, epoxy that obtains, add solidifying agent (DICY) and curing catalyst (2E4MZ), carry out the veneer sheet evaluation by aforesaid method with the ratio shown in the table 1.Its result is as shown in table 1.
Embodiment 2
Except using HCA84.5 weight part, 1,4-naphthoquinones 51.7 weight parts, toluene 127 weight parts, ESN-485 663.0 weight parts, triphenylphosphine 0.1 weight part, outside ESN-485 cooperates the EPPN-501H (the system trifunctional epoxy resin of Nippon Kayaku K. K) of 200.8 weight parts simultaneously, carry out 1 identical operations with embodiment.Mol ratio is 1,4-naphthoquinones/HCA=0.83.The epoxy equivalent (weight) of the Resins, epoxy that obtains is 346.7g/eq, and phosphorus content is 1.2 weight %.The GPC of the Resins, epoxy that obtains, FTIR are as shown in Figure 1 and Figure 2.In addition, in the Resins, epoxy that obtains, add solidifying agent (DICY) and curing catalyst (2E4MZ), carry out the veneer sheet evaluation by aforesaid method with the ratio shown in the table 1.Its result is as shown in table 1.
Embodiment 3
Except using HCA is 70.1 weight parts, 1, and 4-naphthoquinones 46.2 weight parts, dimethylbenzene 235 weight parts, to substitute ESN-155 that ESN-485 uses 209.8 weight parts, make triphenylphosphine be outside 0.1 weight part, carries out 1 identical operations with embodiment.Mol ratio is 1,4-naphthoquinones/HCA=0.900.The epoxy equivalent (weight) of the Resins, epoxy that obtains is 326.1g/eq, and phosphorus content is 1.0 weight %.
In the Resins, epoxy that obtains, add solidifying agent (DICY) and curing catalyst (2E4MZ), carry out the veneer sheet evaluation by aforesaid method with the ratio shown in the table 1.Its result is as shown in table 1.
Embodiment 4
Except making HCA be 9.0 weight parts, substitute 1, the 4-naphthoquinones uses the HCA-HQ of 70.0 weight parts, alternative ESN-485 to use the ESN-155 of 721.0 weight parts, cooperates simultaneously outside the ESN-375 of 200.0 weight parts, carries out 1 identical operations with embodiment.The epoxy equivalent (weight) of the Resins, epoxy that obtains is 274.9g/eq, and phosphorus content is 0.8 weight %.
In the Resins, epoxy that obtains, add solidifying agent (DICY) and curing catalyst (2E4MZ), carry out the veneer sheet evaluation by aforesaid method with the ratio shown in the table 1.Its result is as shown in table 1.
Comparative example 1
Except using HCA 127.0 weight parts, dihydroxyphenyl propane (Nippon Steel Chemical Co., Ltd's system) 62.1 weight parts, エ ボ ト one ト YDPN-638 (Toto Kasei KK's system, the phenol novolac epoxy resin) outside 810.9 weight parts, triphenylphosphine 0.2 weight part, carries out 1 identical operations with embodiment.The epoxy equivalent (weight) of the Resins, epoxy that obtains is 298.6g/eq, and phosphorus content is 1.8 weight %.
In the Resins, epoxy that obtains, add solidifying agent (DICY) and curing catalyst (2E4MZ), carry out the veneer sheet evaluation by aforesaid method with the ratio shown in the table 1.Its result is as shown in table 1.
Comparative example 2
Except using HCA 70.5 weight parts, dihydroxyphenyl propane 64.7 weight parts, エ ボ ト one ト YDCN-701 (Toto Kasei KK's system, the cresols novolac epoxy resin) outside 864.8 weight parts, triphenylphosphine 0.1 weight part, carries out 1 identical operations with embodiment.Mol ratio is 1,4-naphthoquinones/HCA=0.93.The epoxy equivalent (weight) of the Resins, epoxy that obtains is 293.7g/eq, and phosphorus content is 1.0 weight %.
In the Resins, epoxy that obtains, add solidifying agent (DICY) and curing catalyst (2E4MZ), carry out the veneer sheet evaluation by aforesaid method with the ratio shown in the table 1.Its result is as shown in table 1.
Comparative example 3
Except using HCA 56.1 weight parts, 1,4-naphthoquinones 37.0 weight parts, dimethylbenzene 235 weight parts, alternative ESN-485 use ZX-1142L (Toto Kasei KK's system, α naphthols novolac epoxy resin) 906.9 weight parts, to make triphenylphosphine be outside 0.1 weight part, carries out 1 identical operations with embodiment.Mol ratio is 1,4-naphthoquinones/HCA=0.90.The epoxy equivalent (weight) of the Resins, epoxy that obtains is 298.9g/eq, and phosphorus content is 0.8 weight %.
In the Resins, epoxy that obtains, add solidifying agent (DICY) and curing catalyst (2E4MZ), carry out the veneer sheet evaluation by aforesaid method with the ratio shown in the table 1.Its result is as shown in table 1.
Comparative example 4
Except using HCA 141.0 weight parts, 1,4-naphthoquinones 77.4 weight parts, toluene 329 weight parts, alternative ESN-485 use YDPN-638631.6 weight part, YDF-170 150.0 weight parts, make triphenylphosphine is outside 0.2 weight part, carries out 1 identical operations with embodiment.Mol ratio is 1,4-naphthoquinones/HCA=0.75.The molar equivalent of the Resins, epoxy that obtains is 306.4g/eq, and phosphorus content is 2.0 weight %.
In the Resins, epoxy that obtains, add solidifying agent (DICY) and curing catalyst (2E4MZ), carry out the veneer sheet evaluation by aforesaid method with the ratio shown in the table 1.Its result is as shown in table 1.
Comparative example 5
Except using HCA 70.4 weight parts, 1,4-naphthoquinones 13.3 weight parts, toluene 164 weight parts, to substitute that ESN-485 uses YDPN-638 249.6 weight parts, makes triphenylphosphine be outside 0.2 weight part, carries out 1 identical operations with embodiment.Mol ratio is 1,4-naphthoquinones/HCA=0.25.The epoxy equivalent (weight) of the Resins, epoxy that obtains is 287.1g/eq, and phosphorus content is 3.0 weight %.
Mix the ESN-485 of resulting Resins, epoxy of 33.3 weight parts and 66.7 weight parts, carry out the veneer sheet evaluation.The veneer sheet evaluation result is as shown in table 1.
Observe the above embodiment and the test-results of comparative example, by the rerum natura of the comparative example record of table 1 as can be known, phosphorus content is to can not get flame retardant resistance at 1% o'clock in the phosphorated novolac epoxy resin.If wish to get flame retardant resistance phosphorus content being increased to 2%, even then thermotolerance improves, also is the degree of comparative example 4, and water-absorbent is poor.On the other hand, importing has in the comparative example 3 of naphthalene skeleton, and phosphorus content is to can not get flame retardant resistance at 0.8% o'clock in the phosphorated naphthols novolac epoxy resin.When cooperating phosphorated novolac epoxy resin and naphthols aralkyl-type epoxy resin, flame retardant resistance, thermotolerance, water-intake rate all do not take effect really.
By technology synthetic neo-epoxy resin of the present invention is the cured article that can obtain flame retardant resistance, high thermotolerance and low water-intake rate at 0.8% o'clock at phosphorus content.Novel phosphorus-containing Resins, epoxy of the present invention like this, novel phosphorus-containing composition epoxy resin have flame retardant resistance under low phosphorus content, and physical properties excellent such as thermotolerance, cementability, water-intake rate, so be suitable for most with the copper plate pressing plate that uses in the electronic circuit board electrically insulating material as representative, the sealing material that is suitable for using in the electronic component, formed material, cast-molding material, caking agent, mould material, and also be effective as electrical insulating coating with material.
Industrial applicibility
The novel containing phosphorus epoxy resins, the novel containing phosphorus epoxy resins composition that obtain by the present invention exist Have anti-flammability under the low phosphorus content, and the physical properties excellent such as heat resistance, cementability, water absorption rate, So be particularly suitable as with the copper-clad laminate that uses in the electronic circuit board exhausted as the electricity of representative The edge material, the encapsulant that uses in the electronic component, moulding material, cast-molding material, bonding agent, Membrane material also is suitable as the electrically-insulating paint material.
Claims (according to the modification of the 19th of treaty)
1. the novel phosphorus-containing Resins, epoxy shown in the general formula (1) with naphthalene skeleton,,
A: the integer of expression 1,2,3, the 1st, necessary,
B: the integer of expression 1,2,3,
c：0、1、2、3、......，
(X) expression benzene, naphthalene, anthracene, phenanthrene, biphenyl,
(Y) at least 1 (Y) is general formula 3 or general formula 4 in 2～4,1 molecule of expression general formula,
D: expression 0 or 1,
R1, R2 represent alkyl, can be straight chain shape, a chain, ring-type, and in addition, R1 and R2 can be in conjunction with the formation ring texturees,
E: the integer of expression 0,1,2,
B: the integer of expression 1,2,3,
g：1、2、3......，
D: expression 0 or 1,
F: the integer of expression 1,2,3,
Wherein, f and e add up to 1～3 integer,
R1, R2 represent alkyl, can be straight chain shape, a chain, ring-type, and in addition, R1 and R2 can be in conjunction with the formation ring texturees,
(X) expression benzene, naphthalene, anthracene, phenanthrene, biphenyl,
(Y) expression general formula 2～4,
(Z) expression general formula 5, general formula 6,
H: the integer of expression 0,1,2,3,
R3: the expression alkyl, can be straight chain shape, a chain, ring-type,
I: the integer of expression 0,1,2,3,4,5,
R3: the expression alkyl can be straight chain shape, a chain, ring-type.
2. novel phosphorus-containing Resins, epoxy as claimed in claim 1 is to be that 1 Resins, epoxy is that the necessary epoxy resin with naphthalene skeleton reacts with the phosphorus compound class shown in general formula (8) and/or the general formula (9) and obtains with a in the general formula (7) and b,
A: the integer of expression 1,2,3,
B: the integer of expression 1,2,3,
c：0、1、2、3、......，
(X) expression benzene, naphthalene, anthracene, phenanthrene, biphenyl,
D: the integer of expression 0 or 1,
R1, R2 represent alkyl, can be straight chain shape, a chain, ring-type, and in addition, R1 and R2 can be in conjunction with the formation ring texturees,
D: the integer of expression 0 or 1,
R1, R2 represent alkyl, can be straight chain shape, a chain, ring-type, and in addition, R1 and R2 can be in conjunction with the formation ring texturees,
(Z) expression general formula 5, general formula 6.
3. phosphorous epoxy resin composition cooperates solidifying agent to form in claim 1 or 2 described phosphorous epoxy resins.
4. epoxy laminate is characterized in that, uses the described phosphorous epoxy resin composition of claim 3.
5. the epoxy sealing material is characterized in that, uses the described phosphorous epoxy resin composition of claim 3.
6. the Resins, epoxy cast-molding material is characterized in that, uses the described phosphorous epoxy resin composition of claim 3.
7. the phosphorous epoxy resin cured article obtains the described phosphorous epoxy resin composition curing of claim 3～6.
Claims (7)
1. the novel phosphorus-containing Resins, epoxy shown in the general formula (1) with naphthalene skeleton,
a：1、2、3、4、5、6，
b：1、2、3、4、5、6、7，
c：0、1、2、3、......，
(X) expression benzene, naphthalene, anthracene, phenanthrene, biphenyl,
(Y) expression general formula (2)～(4), at least 1 (Y) is general formula (3) or general formula (4) in 1 molecule,
D:0 or 1,
R1, R2 represent alkyl, can be straight chain shape, a chain, ring-type, and in addition, R1 and R2 can be in conjunction with the formation ring texturees,
e：0、1、2、3、4、5、6，
b：1、2、3、4、5、6、7，
g：1、2、3......，
D:0 or 1,
f：1、2、3、4、5、6，
f+e≤6
R1, R2 represent alkyl, can be straight chain shape, a chain, ring-type, and in addition, R1 and R2 can be in conjunction with the formation ring texturees,
(X) expression benzene, naphthalene, anthracene, phenanthrene, biphenyl,
(Y) expression general formula 2～4,
(Z) expression general formula 5, general formula 6,
h：0、1、2、3，
R3: the expression alkyl, can be straight chain shape, a chain, ring-type,
i：0、1、2、3、4、5，
R3: the expression alkyl can be straight chain shape, a chain, ring-type.
2. novel phosphorus-containing Resins, epoxy as claimed in claim 1 obtains by the reaction of the phosphorus compound class shown in the epoxy resin with naphthalene skeleton shown in the general formula (7) and general formula (8) and/or the general formula (9),
a：1、2、3、4、5、6，
b：1、2、3、4、5、6、7，
c：0、1、2、3、......，
(X) expression benzene, naphthalene, anthracene, phenanthrene, biphenyl,
D:0 or 1,
R1, R2 represent alkyl, can be straight chain shape, a chain, ring-type, and in addition, R1 and R2 can be in conjunction with the formation ring texturees,
D:0 or 1,
R1, R2 represent alkyl, can be straight chain shape, a chain, ring-type, and in addition, R1 and R2 can be in conjunction with the formation ring texturees,
(Z) expression general formula 5, general formula 6.
3. phosphorous epoxy resin composition cooperates solidifying agent to form in claim 1 or 2 described phosphorous epoxy resins.
4. epoxy laminate is characterized in that, uses the described phosphorous epoxy resin composition of claim 3.
5. the epoxy sealing material is characterized in that, uses the described phosphorous epoxy resin composition of claim 3.
6. the Resins, epoxy cast-molding material is characterized in that, uses the described phosphorous epoxy resin composition of claim 3.
7. the phosphorous epoxy resin cured article obtains the described phosphorous epoxy resin composition curing of claim 3～6.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007054780A JP5334373B2 (en) | 2007-03-05 | 2007-03-05 | Novel phosphorus-containing epoxy resin, epoxy resin composition containing epoxy resin as an essential component, and cured product thereof |
| JP054780/2007 | 2007-03-05 | ||
| PCT/JP2008/054248 WO2008108485A1 (en) | 2007-03-05 | 2008-03-04 | Novel phosphorus-containing epoxy resin, epoxy resin composition essentially containing the epoxy resin, and cured product of the epoxy resin composition |
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| Publication Number | Publication Date |
|---|---|
| CN101679601A true CN101679601A (en) | 2010-03-24 |
| CN101679601B CN101679601B (en) | 2014-06-25 |
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| CN200880007011.5A Expired - Fee Related CN101679601B (en) | 2007-03-05 | 2008-03-04 | Novel phosphorus-containing epoxy resin, epoxy resin composition essentially containing the epoxy resin, and cured product of the epoxy resin composition |
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| Country | Link |
|---|---|
| US (1) | US8057902B2 (en) |
| EP (1) | EP2123688A4 (en) |
| JP (1) | JP5334373B2 (en) |
| CN (1) | CN101679601B (en) |
| TW (1) | TWI457358B (en) |
| WO (1) | WO2008108485A1 (en) |
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| CN103102470A (en) * | 2011-11-11 | 2013-05-15 | 新日铁住金化学株式会社 | Flame-retardant epoxy resin, epoxy resin composition containing the epoxy resin as essential component and cured product thereof |
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| JP5376767B2 (en) * | 2007-03-26 | 2013-12-25 | 新日鉄住金化学株式会社 | Novel thermoplastic polyhydroxy polyether resin and resin composition containing the same |
| KR101055683B1 (en) | 2008-12-26 | 2011-08-09 | 제일모직주식회사 | Novel phosphonate compound and flame retardant styrene resin composition comprising same |
| KR101095225B1 (en) * | 2009-04-23 | 2011-12-20 | 삼성전기주식회사 | Resin composition for printed circuit board and printed circuit board using the same |
| JP5341679B2 (en) * | 2009-08-31 | 2013-11-13 | 株式会社日立製作所 | Semiconductor device |
| JP5579008B2 (en) * | 2010-09-29 | 2014-08-27 | 新日鉄住金化学株式会社 | Phosphorus-containing epoxy resin |
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| JP3613724B2 (en) * | 1997-09-09 | 2005-01-26 | 東都化成株式会社 | Phosphorus-containing epoxy resin composition |
| JP3533973B2 (en) * | 1998-01-27 | 2004-06-07 | 東都化成株式会社 | Phosphorus-containing epoxy resin composition |
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| US6486242B1 (en) * | 1999-04-20 | 2002-11-26 | Sumitomo Bakelite Company Limited | Flame-retardant resin composition and prepreg and laminate using the same |
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| TW587094B (en) * | 2000-01-17 | 2004-05-11 | Sumitomo Bakelite Co | Flame-retardant resin composition comprising no halogen-containing flame retardant, and prepregs and laminates using such composition |
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- 2008-03-04 EP EP08721664.4A patent/EP2123688A4/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103102470A (en) * | 2011-11-11 | 2013-05-15 | 新日铁住金化学株式会社 | Flame-retardant epoxy resin, epoxy resin composition containing the epoxy resin as essential component and cured product thereof |
| CN103102470B (en) * | 2011-11-11 | 2016-09-07 | 新日铁住金化学株式会社 | Fire-retarded epoxy resin and be the required composition of composition, solidfied material with this epoxy resin |
Also Published As
| Publication number | Publication date |
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| US8057902B2 (en) | 2011-11-15 |
| EP2123688A4 (en) | 2013-12-18 |
| CN101679601B (en) | 2014-06-25 |
| TWI457358B (en) | 2014-10-21 |
| JP5334373B2 (en) | 2013-11-06 |
| US20100093928A1 (en) | 2010-04-15 |
| WO2008108485A1 (en) | 2008-09-12 |
| JP2008214513A (en) | 2008-09-18 |
| TW200902580A (en) | 2009-01-16 |
| EP2123688A1 (en) | 2009-11-25 |
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